A method for the preparation of 1,2-propanediol

ABSTRACT

A method for preparing 1,2-propanediol involves reacting propene with hydrogen peroxide in the presence of a catalyst mixture, containing a phase transfer catalyst and a heteropolytungstate, in a liquid reaction mixture containing an aqueous phase with a maximum apparent pH of 6 and an organic phase. The method then involves separating the reaction mixture into an aqueous phase (Pa), containing 1,2-propanediol and phosphoric acid esters of 1,2-propanediol, and an organic phase (Po). The method further involves recycling at least part of the separated organic phase (Po) to the reaction; heating at least a part of the separated aqueous phase (Pa) to a temperature of more than 140° C. at a pressure sufficient to maintain at least part of the aqueous phase as a liquid; and recovering 1,2-propanediol from the heated aqueous phase. The heating cleaves phosphoric acid esters of 1,2-propanediol into 1,2-propanediol and phosphoric acid.

FIELD OF THE INVENTION

The present invention relates to a method for the preparation of1,2-propanediol by reacting propene with hydrogen peroxide wherein theamount of phosphoric ester of 1,2-propanediol can be reduced.

BACKGROUND OF THE INVENTION

In a well-established process used in the industry, 1,2-propanediol isprepared by reacting propene oxide with water. Propene oxide can be madeon an industrial basis using the HPPO process comprising the reaction ofpropene with hydrogen peroxide in the presence of a titanium zeolitecatalyst and an organic solvent. Propene oxide is then isolated andpurified prior to the step of reacting it with water to make1,2-propanediol.

WO 2017/089075 discloses a method for producing 1,2-propanediol frompropene and hydrogen peroxide comprising: a) reacting propene withhydrogen peroxide in the presence of a catalyst mixture comprising aphase transfer catalyst and a heteropolytungstate, wherein the reactionis carried out in a liquid mixture comprising an aqueous phase with amaximum pH of 6 and an organic phase, b) dividing the two-phase mixturefrom step a) into an aqueous phase and an organic phase containingpropylene oxide, c) returning the propylene oxide contained in theseparated organic phase into the reaction from step a) and d) separating1,2-propanediol from the aqueous phase separated in step b).

SUMMARY OF THE INVENTION

The inventor of the present invention has now found that in the methoddescribed in WO 2017/089075, phosphoric acid esters of 1,2-propanediolare formed in reaction step a) in a side reaction by reaction of propeneoxide with phosphoric acid present in the reaction mixture. The inventorhas also found that the selectivity for 1,2-propanediol can be improvedby heating all or a part of the aqueous phase separated from theoxidation reaction mixture to a temperature of more than 140° C. at apressure sufficient to maintain a substantial part of the water as aliquid phase, which hydrolyzes the phosphoric acid esters of1,2-propanediol to give 1,2-propanediol.

Subject of the invention is therefore a method for the preparation of1,2-propanediol comprising:

-   -   a) reacting propene with hydrogen peroxide in the presence of a        catalyst mixture comprising a phase transfer catalyst,        phosphoric acid and a heteropolytungstate in a liquid reaction        mixture comprising an aqueous phase with a maximum apparent pH        of 6 and an organic phase;    -   b) separating the reaction mixture into an aqueous phase (P_(a))        comprising 1,2-propanediol and phosphoric acid esters of        1,2-propanediol and an organic phase (P_(o));    -   c) recycling at least a part of the separated organic phase        (P_(o)) to the reaction step a);    -   d) heating at least a part of the aqueous phase (P_(a))        separated in step b) to a temperature of more than 140° C. at a        pressure sufficient to maintain at least 20% by weight of the        water of said aqueous phase (P_(a)) in a liquid phase; and    -   e) recovering 1,2-propanediol from the aqueous phase heated in        step d).

In a further aspect the present invention relates to the use of aheating step d) to cleave phosphoric acid esters of 1,2-propanediol into1,2-propanediol and phosphoric acid in a method for the preparation of1,2-propanediol comprising:

-   -   a) reacting propene with hydrogen peroxide in the presence of a        catalyst mixture comprising a phase transfer catalyst,        phosphoric acid and a heteropolytungstate in a liquid reaction        mixture comprising an aqueous phase with a maximum apparent pH        of 6 and an organic phase;    -   b) separating the reaction mixture into an aqueous phase (P_(a))        comprising 1,2-propanediol and phosphoric acid esters of        1,2-propanediol and an organic phase (P_(o));    -   c) recycling at least a part of the separated organic phase        (P_(o)) to the reaction step a);    -   d) heating at least a part of the aqueous phase (P_(a))        separated in step b) to a temperature of more than 140° C. at a        pressure sufficient to maintain at least 20% by weight of the        water of said aqueous phase (P_(a)) in a liquid phase; and    -   e) recovering 1,2-propanediol from the aqueous phase heated in        step d).

DETAILED DESCRIPTION OF THE INVENTION

In the method of the present invention, propene is reacted in a step a)with hydrogen peroxide in the presence of a catalyst mixture comprisinga phase transfer catalyst and a heteropolytungstate. This reaction iscarried out in a liquid reaction mixture which comprises an aqueousphase with a maximum apparent pH of 6 and an organic phase.

Propene can be used in pure form or in a mixture with propane, whereinthe proportion of propane may be up to 20 mol-%. The proportion ofpropane in the propene used is preferably less than 5 mol-%. Propene ispreferably employed in a molar excess to hydrogen peroxide, preferablyin a molar ratio of propene to hydrogen peroxide of from 1.1:1 to 10:1.

Hydrogen peroxide is preferably used in the form of an aqueous solution,preferably with a hydrogen peroxide content of 10 to 80% by weight,particularly preferably 30 to 70% by weight. Any commercially availablegrade of aqueous hydrogen peroxide solutions can be used. A crudehydrogen peroxide product obtained in the extraction stage of theanthraquinone process for producing hydrogen peroxide may also be used.

The catalyst mixture used in step a) comprises a heteropolytungstate.The heteroatom is preferably phosphorus or arsenic and is particularlypreferably phosphorus, i.e. the heteropolytungstate is particularlypreferably a polytungstophosphate. Heteropolytungstates are well knownto a person skilled in the art. Preferred polytungstophosphates have amolar ratio of phosphorus to tungsten in the range of from 1:2 to 1:12.The polytungstophosphate is preferably generated in situ by combiningphosphoric acid and sodium tungstate, which can be carried out in theliquid reaction mixture itself or prior to adding thepolytungstophosphate to the liquid reaction mixture. Phosphoric acid andsodium tungstate are preferably employed at a molar ratio of phosphorusto tungsten in the range of from 1:2 to 10:1, preferably from 4:1 to8:1. The heteropolytungstate reacts with hydrogen peroxide in the liquidreaction mixture to form peroxotungstates and peroxotungstophosphates,for example PO₄[WO(O₂)₂]₄ ³⁻ and HPO₄[WO(O₂)₂]₂ ³⁻ as well as partiallyprotonated forms thereof, which are presumably the catalytically activespecies for oxidizing propene.

The catalyst mixture used in step a) also comprises a phase transfercatalyst. The phase transfer catalyst comprises a cation or a compoundwhich forms a cation in the aqueous phase, whereby the cation can form asalt with a peroxotungstate or heteropolyperoxotungstate, which salt issoluble in the organic phase of the liquid reaction mixture. The phasetransfer catalyst preferably comprises a singly-charged cation or acompound which forms a singly-charged cation in the aqueous phase.Suitable as phase transfer catalyst are tertiary amines, tertiary andquaternary ammonium salts, and quaternary phosphonium salts. Suitablecounterions for tertiary and quaternary ammonium salts are the anionschloride, bromide, nitrate, sulphate, hydrogen phosphate, dihydrogenphosphate, methyl sulfonate, methyl sulphate and ethyl sulphate. Thephase transfer catalyst is preferably used in an amount which results ina molar ratio in the liquid mixture of phase transfer catalyst totungsten in the range of from 0.2:1 to 3:1 and particularly preferablyof from 0.4:1 to 1:1, where the molar ratio refers to the cations orcompounds forming cations in the employed phase transfer catalyst and tothe employed amount of tungsten.

In a preferred embodiment, the phase transfer catalyst is a tertiaryamine or a tertiary or a quaternary ammonium salt which comprises intotal at least 12 carbon atoms, preferably from 12 to carbon atoms.Preferred are tetraalkylammonium salts. Suitable tertiary amines are forexample dodecyldimethylamine, hexadecyldimethylamine,octadecyldimethylamine, tributylamine and trioctylamine. Suitabletertiary ammonium salts are the protonation products of these teriaryamines. Suitable quaternary ammonium salts are for exampledodecyltrimethylammonium salts, hexadecyltrimethylammonium salts,octadecyltrimethylammonium salts, methyltributylammonium salts andmethyltrioctylammonium salts. More preferably, the phase transfercatalyst comprises a tertiary or quaternary ammonium ion having thestructure R¹R²R³NR⁴⁺, wherein R¹, R² and R³ are the same or differentand are each selected from alkyl groups having from 8 to 10 carbon atomsand R⁴ is hydrogen or methyl. Most preferably, the phase transfercatalyst comprises methyltri(octyl/decyl)ammonium methylsulfate (CAS No.2387913-24-6).

In another preferred embodiment, the phase transfer catalyst comprisesat least one salt having a tertiary or quaternary ammonium ion of thestructure R¹R²R³R⁴N⁺, where R¹ is a Y—O(C═O)R⁵ group with Y beingCH₂CH₂, CH(CH₃)CH₂ or CH₂CH(CH₃) and R⁵ being an alkyl group or alkenylgroup having 11 to 21 carbon atoms,

-   -   R² is hydrogen or an alkyl group having 1 to 4 carbon atoms, and    -   R³ and R⁴ are each independently R¹, an alkyl group having 1 to        4 carbon atoms or Y—OH. Preferred are quaternary ammonium salts        with methylsulphate as the counterion, where R² is a methyl        group and R⁵ is a linear alkyl group or alkenyl group.        Particularly preferred are the salts (CH₃)₃N⁺CH₂CH₂O(C═O)R⁵        CH₃OSO₃ ⁻, (CH₃)₂N⁺(CH₂CH₂OH)(CH₂CH₂O(C═O)R⁵) CH₃OSO₃ ⁻,        (CH₃)₂N⁺(CH₂CH₂O(C═O)R⁵)₂ CH₃OSO₃ ⁻,        CH₃N⁺(CH₂CH₂OH)₂(CH₂CH₂O(C═O)R⁵) CH₃OSO₃ ⁻,        CH₃N⁺(CH₂CH₂OH)(CH₂CH₂O(C═O)R⁵)₂ CH₃OSO₃ ⁻,        CH₃N⁺(CH₂CH₂O(C═O)R⁵)₃ CH₃OSO₃ ⁻, (CH₃)₃N⁺CH₂CH(CH₃)O(C═O)R⁵        CH₃OSO₃ ⁻, (CH₃)₂N⁺(CH₂CH(CH₃)OH)(CH₂CH(CH₃)O(C═O)R⁵) CH₃OSO₃ ⁻        and (CH₃)₂N⁺(CH₂CH(CH₃)O(C═O)R⁵)₂ CH₃OSO₃ ⁻, in which R⁵ is in        each case a linear alkyl group or alkenyl group having 11 to 21        carbon atoms. Most preferred is the salt        (CH₃)₂N⁺(CH₂CH(CH₃)O(C═O)R⁵)₂ CH₃OSO₃ ⁻ in which R⁵ is an alkyl        group or alkenyl group having 11 to 17 carbon atoms. The phase        transfer catalysts of this embodiment may be prepared by        esterifying ethanolamine, isopropanolamine, diethanolamine,        diisopropanolamine, triethanolamine or triisopropanolamine with        a fatty acid and subsequent quaternization with dimethyl        sulphate.

These phase transfer catalysts have the advantage that they are readilybiodegradable, unlike tetraalkylammonium salts, and can be introducedinto a biological treatment plant without further pretreatment. Thesalts with methylsulphate as anion are also less corrosive thantetraalkylammonium halides.

The reaction of step a) is carried out in a liquid reaction mixturewhich comprises two liquid phases, an aqueous phase with a maximumapparent pH of 6 and an organic phase. The term “apparent pH” hererefers to a value determined by measurement with a glass electrodeemploying a commercial pH meter calibrated with aqueous buffer solutionsof known pH for measuring dilute aqueous solutions. This apparent pHdiffers from the notional pH, i.e. the negative logarithm of thehydrogen ion activity, by a constant value because the normal potentialof the glass electrode in the aqueous phase of the reaction mixture,which comprises hydrogen peroxide and glycols, is different than thenormal potential in pure water. The apparent pH of the aqueous phase ispreferably maintained in the range from 1.0 to 3.5, particularlypreferably in the range from 2.0 to 3.0. The apparent pH can bemaintained in this range by addition of acid, preferably sulphuric acidor phosphoric acid, or by addition of base, preferably aqueous sodiumhydroxide solution. Adjusting the apparent pH in the preferred rangeprovides high selectivity for 1,2-propanediol and prevents enrichingpropene oxide in the aqueous phase, which simplifies the subsequentseparation of propylene glycols from the aqueous phase.

In the reaction step a) the weight ratio of hydrogen peroxide to waterfed to step a) is preferably adjusted while maintaining a molar excessof propene to hydrogen peroxide fed to step a). The weight ratio ofhydrogen peroxide to water is preferably varied within the range of from0.05 to 1.5, more preferably from 0.10 to 0.7 and most preferably from0.15 to 0.45. The molar ratio of propene to hydrogen peroxide fed tostep a) is preferably from 1.1:1 to 10:1, more preferably from 1.2:1 to4:1.

The reaction is preferably conducted at a temperature in the range offrom 50 to 110° C., more preferably 60 to 100° C. and particularlypreferably 70 to 90° C. The reaction pressure is preferably higher thanthe vapor pressure of propene at the reaction temperature to ensure thatmost of the propene is present in the liquid organic phase of the liquidmixture.

The reaction of step a) can be carried out with or without addition ofan organic solvent. The reaction is preferably conducted in the presenceof at least one organic solvent having a boiling point of more than 100°C., preferably more than 120° C., which has a solubility in water ofless than 250 mg/kg at 20° C. Suitable as solvents are alcohols havingone or more hydroxyl groups, ethers, esters, ketones and alkylatedaromatic hydrocarbons. Adding a solvent can improve extraction of a saltformed of the heteropolytungstate and the phase transfer catalyst intothe organic phase. Preferably the amount of organic solvent is selectedto provide a proportion of organic solvent in the organic phase duringthe reaction in the range of from 10 to 90% by weight.

In a preferred embodiment, the organic solvent comprises an epoxidizedfatty acid methyl ester. The epoxidized fatty acid methyl ester can beformed in situ in the reaction mixture of step a) by employing a fattyacid methyl ester with unsaturated fatty acid groups which reacts withhydrogen peroxide to the epoxidized fatty acid methyl ester.Particularly preferred are epoxidized fatty acid methyl esters whichcomprise fatty acid groups originating from vegetable oils, inparticular soybean oil. The epoxidized fatty acid methyl esters have theadvantage that they have low solubility in the aqueous phase.

In another preferred embodiment, the solvent comprises an alkylatedaromatic hydrocarbon having 8 to 12 carbon atoms. Suitable alkylatedaromatic hydrocarbons are, for example, 1,2-dimethylbenzene (o-xylene),1,3-dimethylbenzene (m-xylene), 1,4-dimethylbenzene (p-xylene),ethylbenzene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene,1,3,5-trimethylbenzene (mesitylene), 1-ethyl-2-methylbenzene,1-ethyl-3-methylbenzene and 1-ethyl-4-methylbenzene and n-propylbenzene.Preferably, hydrocarbon mixtures comprising more than 50% by weight,particularly preferably more than 80% by weight, of alkylated aromatichydrocarbons having 8 to 12 carbon atoms are used as solvent. The use ofthese solvents enables extracting most of the peroxotungstates into theorganic phase of the reaction mixture and recycling them, which allowsfor operating the process without a need for recoveringheteropolytungstate from the aqueous phase of the reaction mixture ofstep a). The phase transfer catalyst, the molar ratio of phase transfercatalyst to heteropolytungstate, the molar ratio of heteroatom of theheteropolytungstate to tungsten, the molar ratio of propene to hydrogenperoxide and the amount of solvent are then preferably selected totransfer as much as possible of the tungsten present in the liquidreaction mixture into the organic phase.

The phase transfer catalyst, the heteropolytungstate and the optionallyused solvent can be added in step a) of the method of the presentinvention separately or in the form of mixtures containing two or allthree of these components. Preferably, a solvent is used in step a) andthe phase transfer catalyst and the heteropolytungstate are addeddissolved in an organic phase comprising the solvent.

The reaction of step a) is carried out in the presence of phosphoricacid. Phosphoric acid is preferably used in an amount providing anapparent pH of the aqueous phase (P_(a)) of the reaction mixture of from1.0 to 3.5, preferably of from 2.0 to 3.0. The concentration ofphosphoric acid and phosphates in the aqueous phase (P_(a)) of thereaction mixture is preferably from 0.2 to 0.8% by weight, calculated asPO₄ ³⁻ relative to the mass of the aqueous phase. Phosphoric acid may bepresent from in situ formation of a polytungstophosphate in the aqueousphase (P_(a)) of the reaction mixture as described above.

The reaction of step a) may be carried out in batch or continuously,with a continuous reaction being preferred. The concentration ofhydrogen peroxide in the aqueous phase is preferably maintained in therange of 0.1 to 5% by weight, particularly preferably 0.5 to 3% byweight. The concentration of hydrogen peroxide can be adjusted in thisrange by appropriate selection of the reaction temperature, the molarratio of propene to hydrogen peroxide and the residence time of theliquid mixture in the reactor in which the reaction takes place. Theresidence time of the reaction mixture is preferably adjusted tomaintain a hydrogen peroxide conversion in the range of from 80 to 99%.

During the reaction, the liquid mixture is preferably mixed in order togenerate a large phase interface between the aqueous phase and theorganic phase. For this purpose, the reaction is preferably carried outcontinuously in a loop reactor which has fixed internals in a tubularsection and the liquid mixture is passed through the loop reactor at aflow rate which generates a turbulent flow at the internals. Baffles,static mixing elements, structured packings or random packings can beused as internals for this purpose. In combination to these internals oras an alternative, heat exchangers, such as plate heat exchangers ortube bundle heat exchangers, may be used, in which turbulent flow isgenerated, for example between the plates of a plate heat exchanger orin the tubes of a tube bundle heat exchanger.

Preferably, all or a part of the reaction heat generated in step a) isremoved while the reaction proceeds, preferably by cooling the reactionmixture in a heat exchanger. More preferably, the reaction is carriedout continuously in a loop reactor which comprises a heat exchangerwithin the reactor loop for cooling the reaction mixture.

In step b) of the method of the present invention, the liquid reactionmixture provided by step a) is separated into an aqueous phase (P_(a))comprising 1,2-propanediol and phosphoric acid esters of 1,2-propanedioland an organic phase (P_(o)). The separation of the two-phase reactionmixture provided by step a) is preferably carried out in a settlervessel. The two-phase reaction mixture is preferably passed through acoalescer element comprising a structured packing or a random packingwith a surface wetted by the dispersed phase of the two-phase mixture inorder to achieve a more complete separation.

The aqueous phase (P_(a)) typically comprises water, unreacted hydrogenperoxide and the reaction product 1,2-propanediol. The aqueous phasetypically also contains dipropylene glycol and tripropylene glycol aswell as reaction byproducts, such as 1-hydroperoxy-2-propanol and2-hydroperoxy-1-propanol formed by reaction of propene oxide withhydrogen peroxide, and formic acid, acetic acid and hydroxyacetoneformed by further oxidation of 1,2-propanediol. The aqueous phase alsocomprises phosphoric acid and phosphoric acid esters of 1,2-propanedioland may further contain sodium salts of phosphoric acid if apolytungstophosphate generated in situ by combining phosphoric acid andsodium tungstate is used in step a). The organic phase (P_(o)) comprisesunreacted propene and propene oxide that is formed as intermediate whenpropene is reacted with hydrogen peroxide and has not been hydrolyzed to1,2-propanediol. The organic phase (P_(o)) typically also comprises oneor more salts formed of the heteropolytungstate and the cation of thephase transfer catalyst. The organic phase P_(o) will also comprisepropane, if the propene starting material contains propane, and organicsolvent, if an organic solvent having a low solubility in water is usedas described further above.

In step c) of the method of the present invention, at least a part ofthe separated organic phase (P_(o)) is recycled to the reaction step a).Thereby, propene oxide present in the organic phase (P_(o)) is recycledto step a) in order to achieve a complete conversion of propene to1,2-propanediol, dipropylene glycol and tripropylene glycol. Preferably,the heteropolytungstate present in the organic phase (P_(o)) is recycledinto step a), and it is particularly preferred to recycle substantiallyall of the catalyst mixture that is present in the organic phase intostep a).

The organic phase (P_(o)) separated from the liquid reaction mixtureprovided by step a) may be recycled to step a) without furthertreatment. If the propene fed to step a) contains propane, it ispreferred to separate a stream of unreacted propene from the organicphase in step c) before the organic phase is recycled to step a), withthe separated stream of unreacted propene containing as much propane asthe impure propene fed to step a). This way, an accumulation of propanein the organic phase of the reaction mixture of step a) can be avoidedfor a continuous reaction. The separated stream of unreacted propene maybe passed to a C3 splitter for separating propene and propane and therecovered propene may be recycled to step a).

The aqueous phase (P_(a)) obtained in step b) is preferably furtherprocessed without recycling any part of it directly or indirectly tostep a).

In step d) of the method of the present invention, at least a part andpreferably all of the aqueous phase (P_(a)) separated in step b) isheated to a temperature of more than 140° C. at a pressure sufficient tomaintain at least 20% by weight of the water of said aqueous phase(P_(a)) in a liquid phase. Preferably, the aqueous phase (P_(a)) isheated to a temperature in the range of 142° C. to 200° C. The pressurein heating step d) may be from 4 to 200 bar and is preferably theautogenous pressure resulting from the vapor pressure of water at thetemperature used in step d). Heating step d) is preferably performedwithout adding hydrogen. The aqueous phase (P_(a)) is preferably heatedin step d) for a time sufficient to hydrolyze more than 30 mol-% of thephosphoric acid esters of 1,2-propanediol, preferably from 50 to 90mol-%, which will typically require from 5 to 60 min. The heating ofstep d) can be carried out in any type of pressure reactor and ispreferably carried out in a plug flow reactor, such as a pipe reactor.

In a preferred embodiment, at least a part and preferably all of theaqueous phase (P_(a)) obtained in step b) is subjected to a step f) ofcatalytic hydrogenation at a temperature of from 80° C. to 140° C.,preferably from 90° C. to 120° C., between steps b) and d) or betweensteps d) and e). The hydrogenation is preferably carried out using asupported hydrogenation catalyst comprising one or more metals from thegroup of Ru, Rh, Pd, Pt, Ag, Ir, Fe, Cu, Ni and Co on a support, whereinactivated carbon, SiO₂, TiO₂, ZrO₂, Al₂O₃ and aluminium silicates arepreferred as support materials. Preference is given to hydrogenationcatalysts comprising ruthenium as active metal. The catalytichydrogenation is preferably carried out at a partial hydrogen pressureof 5 to bar, preferably 5 to 35 bar, more preferred 7 to 30 bar, evenmore preferred 8 to 25 bar. The hydrogenation catalyst may be used as asuspension or as a fixed bed, a trickle bed hydrogenation with a fixedbed catalyst being preferred. The hydrogenation can prevent problemscaused by decomposition of hydrogen peroxide, which has not reacted instep a), in step e) of recovering 1,2-propanediol and dipropyleneglycol. The hydrogenation also converts the by-products1-hydroperoxy-2-propanol, 2-hydroperoxy-1-propanol and hydroxyacetoneformed in step a) to 1,2-propanediol and thereby improves the yield of1,2-propanediol. Preferably, step f) of catalytic hydrogenation iscarried out between steps b) and d) to prevent decomposition of hydrogenperoxide or hydroperoxide by-products in heating step d).

In step e) of the method of the present invention, 1,2-propanediol isrecovered from the heat treated and optionally hydrogenated aqueousphase (P_(a)), preferably by distillation. Preferably, 1,2-propanedioland higher propylene glycols, like dipropylene glycol and tripropyleneglycol, are recovered by a sequence of distillation steps, such as amulti-step distillation with the first distillation step and optionallyfurther distillation steps providing an overhead product comprisingwater and a bottoms product which is passed to the next distillationstep, and a distillation step providing an overhead product comprising1,2-propanediol and a residuals bottoms product which is preferablysubjected to at least one further distillation step. Most preferably, asequence of distillation steps as described in Ullmann's Encyclopedia ofIndustrial Chemistry, online edition, entry “Propanediols”, page 4, DOI10.1002/14356007.a22_163. pub2 is used where an overhead productcomprising water is separated from a bottoms product comprising1,2-propanediol and higher propylene glycols in a series of two to fourheat integrated distillation steps, followed by a vacuum distillationstep which provides 1,2-propanediol as the overhead product and abottoms product containing higher boiling organic compounds and salts.From this bottoms product, dipropylene glycol and tripropylene glycolmay be recovered as overhead products in further vacuum distillationsteps. In a preferred embodiment, the heated aqueous phase obtained instep d) is directly fed to a distillation step where an overhead productcomprising water is separated in order to use the heat supplied in stepd) for recovering 1,2-propanediol in step e).

Heating all or a part of the separated aqueous phase (P_(a)) prior torecovering 1,2-propanediol increases the yield of 1,2-propanediol byconverting the phosphoric acid esters of 1,2-propanediol, which areunwanted by-products, to the desired product 1,2-propanediol.

The present invention will now be explained in more detail withreference to an example.

Example Preparation of Initial Epoxidation Catalyst Solution

A mixture of 86 g 70% by weight hydrogen peroxide, 98 g demineralizedwater, 207 g 85% by weight phosphoric acid and 129 g sodium tungstatedihydrate was stirred for 2 h at room temperature. Then, a solution of194 g of methyltri(octyl/decyl)ammonium methylsulfate (CAS No.2387913-24-6) in 800 g Hydrosol A 200 ND (a mixture of C10 alkylbenzenes) was added and the mixture was stirred for another 2 h at roomtemperature. The aqueous and organic phases were then separated toprovide 1067 g of organic phase as initial epoxidation catalystsolution.

Reaction of Propene with Hydrogen Peroxide

The reaction of propene with hydrogen peroxide was carried out at atemperature of 80° C. and a pressure of 30 bar in a loop reactor with aloop volume of 0.45 l, a circulation pump and a heat exchanger foradjusting the reaction temperature, which was operated at a circulationrate of 130 kg h⁻¹. The reactor was equipped with a catalyst feedreservoir and feed pumps for feeding liquid propene, liquid propane, anaqueous hydrogen peroxide solution and liquid from the catalyst feedreservoir. The initial epoxidation catalyst solution was charged to thecatalyst feed reservoir. The loop initially contained reaction mixturefrom a previous experiment. Circulation was started and maintained at130 kg h⁻¹ and the circulating mixture was heated to 80° C. Then 80 gh⁻¹ of propene, 50 g h⁻¹ of propane, 210 g h⁻¹ of a 15% by weightaqueous hydrogen peroxide solution containing 0.3% by weight phosphoricacid, and 320 g h⁻¹ of organic catalyst solution from the catalyst feedreservoir were introduced into the loop reactor, cooling the circulatingmixture to maintain a reaction temperature of 80° C. A two-phaseoxidation reaction mixture was removed from the loop reactor in anamount corresponding to the amounts added and 18 g h⁻¹ of a 4.8% byweight aqueous disodium sulfate solution was added to this mixture atthe reactor outlet to speed up phase separation. The organic phase andthe aqueous phase of the resulting mixture were separated, and theorganic phase was passed to the catalyst feed reservoir afterdepressurizing and cooling to 25° C. After about 11 h of operation, thefeeding of reactants and the circulation in the loop reactor werestopped. The next day, circulation in the loop reactor was restarted,dosing of reactants was resumed after the reaction temperature had beenestablished in the loop reactor and the reaction was continued foranother 11 h. Aqueous phase for further hydrogenation and heat treatmentwas collected after a stationary operating state was reached.

Hydrogenation of the Separated Aqueous Phase

504 g of the aqueous phase separated from the reaction mixture ofreacting propene with hydrogen peroxide were charged to a 1 l spinningbasket autoclave containing 75 g of a 2% by weight ruthenium onactivated carbon supported catalyst in the spinning basket. Theautoclave was flushed with nitrogen followed by hydrogen andhydrogenation was carried out at 120° C. and 1.6 MPa hydrogen pressurefor 5 h with the basket spinning.

Heat Treatment of the Hydrogenated Aqueous Phase

50 g of the hydrogenated aqueous phase having a pH of 7 were added to a300 ml autoclave. After flushing with nitrogen the autoclave content washeated to 180° C. and held at this temperature for 15 min at a nitrogenpressure of 15 bar. The autoclave was then cooled to ambient temperatureand depressurized.

Prior to and after the heat treatment the aqueous phase was analyzed for1,2-propanediol (MPG), dipropylene glycol (DPG) and tripropylene glycol(TPG) by capillary GC (25 m CP-WAX-52 CB column from Agilent, He carriergas, temperature program starting at 50° C. with ramps of 20 K/min to90° C., 10 K/min to 220° C. and 5 K/min to 235° C., FID detector). Table1 shows the analysis data. Ion chromatography with a conductivitydetector (Metrohm A Supp 5-250 column (polyvinyl alcohol with quaternaryammonium groups), 0.5 ml/min aqueous eluent with 1 mmol/l NaHCO₃ and 3.2mmol/l Na₂CO₃, aqueous suppressor regenerant with 100 mmol/I sulfuricacid and 20 mmol/l oxalic acid) showed that the heat treatment decreasedthe area of the peak associated to propanediol mono phosphoric acidester to 23% of the area prior to heat treatment.

TABLE 1 Propylene glycol contents in % by weight prior to and after theheat treatment prior to heat treatment after heat treatment MPG 22.723.7 DPG 3.2 3.4 TPG 0.3 0.3

1-13. (canceled) 14: A method for the preparation of 1,2-propanediol,comprising: a) reacting propene with hydrogen peroxide in the presenceof a catalyst mixture comprising a phase transfer catalyst, phosphoricacid, and a heteropolytungstate, in a liquid reaction mixture comprisingan aqueous phase with a maximum apparent pH of 6 and an organic phase,wherein apparent pH refers to a value determined by measurement with aglass electrode employing a commercial pH meter calibrated with aqueousbuffer solutions of known pH for measuring dilute aqueous solutions; b)separating the liquid reaction mixture into an aqueous phase (P_(a))comprising 1,2-propanediol and phosphoric acid esters of1,2-propanediol, and an organic phase (P_(o)); c) recycling at least apart of the organic phase (P_(o)) to a); d) heating at least a part ofthe aqueous phase (P_(a)) separated in h) to a temperature of more than140° C. at a pressure sufficient to maintain at least 20% by weight ofwater of said aqueous phase (P_(a)) in a liquid phase, wherein d) isperformed without adding hydrogen; and e) recovering the 1,2-propanediolfrom the at least a part of the aqueous phase (P_(a)) heated in d). 15:The method of claim 14, wherein between h) and d) or between d) and e),at least a part of the aqueous phase (P_(a)) is subjected to a catalytichydrogenation at a temperature of from 80 to 140° C. 16: The method ofclaim 14, wherein in d), the aqueous phase (P_(a)) is heated to atemperature in the range of 142° C. to 200° C. 17: The method of claim14, wherein the pressure in d) is from 4 to 200 bar. 18: The method ofclaim 14, wherein e) comprises a multi-step distillation, with a firstdistillation step and optionally further distillation steps providing anoverhead product comprising water and a bottoms product which is passedto a next distillation step, and a subsequent distillation stepproviding an overhead product comprising the 1,2-propanediol and aresiduals bottoms product. 19: The method of claim 18, wherein theresiduals bottoms product is subjected to at least one furtherdistillation step. 20: The method of claim 14, wherein theheteropolytungstate is a polytungstophosphate. 21: The method of claim14, wherein the organic phase in a) comprises an organic solvent havinga boiling point of more than 100° C. at atmospheric pressure and asolubility in water at 20° C. of less than 250 mg/kg. 22: The method ofclaim 14, wherein the phase transfer catalyst comprises at least oneselected from the group consisting of a tertiary amine, a tertiaryammonium salt, and a quaternary ammonium salt; and wherein the tertiaryamine, the tertiary ammonium salt, and the quaternary ammonium saltcomprises in total at least 12 carbon atoms. 23: The method of claim 22,wherein the phase transfer catalyst comprises a tertiary or quaternaryammonium ion having the structure R¹R²R³NR⁴⁺, wherein R¹, R², and R³ arethe same or different and are each an alkyl group having from 8 to 10carbon atoms, and R⁴ is hydrogen or methyl. 24: The method of claim 14,wherein in d), the phosphoric acid esters of 1,2-propanediol are cleavedinto 1,2-propanediol and phosphoric acid. 25: The method of claim 15,wherein the catalytic hydrogenation is at a temperature of from 90° to120° C. 26: The method of claim 21, wherein the organic solvent is analkylated aromatic hydrocarbon having 8 to 12 carbon atoms.